Organosilsesquioxanes

ABSTRACT

Solventless, time-stable, polymerizable polycondensates of at least 75 mol. percent RSiO1.5 units where R is methyl, vinyl or a hydrogen atom and up to 25 mol. percent of the units are SiO2, (CH3)2SiO, CH3(H)SiO or (CH3)3SiO0.5, are useful intermediates which react with other silicones and organic polymers to find use in making electrical insulation, laminating compounds and molding compounds.

United States Patent [72] Inventors Pierre A. Pruvost;

Michel L. Bourbon; Michel Vialle, all of Rhone, France [21 Appl. No. 876,557

[22] Filed Nov. 13, 1969 [45] Patented Nov. 30, 1971 [73] Assignee Soclete lndustrielle des Sllicones Paris, France [32] Priority June 29, 1965 [3 3 France Original application Feb. 26, 1969, Ser. No. 804,366, now Patent No. 3,489,782, dated Dec. 13, 1970. which is a continuation of application Ser. No. 558,614, June 20, 1966, now abandoned. Divided and this application Nov. 13, 1969, Ser. No. 876,557

[54] ORGANOSILSESQUIOXANES 22 Claims, No Drawings [52] U.S. Cl ..260/46.5 VA, 117/161 ZA, 252/63.7 R. 260/30.4 SB,

260/3 1 .2 R, 260/33.2 SB. 260/33.4 SB, 260/33.6

SB, 260/33.8 SB, 260/46.5 R, 260/465 H,

[51] int. Cl C08i 11/04 [50] Field of Search 260/465, 448.2. 825, 46.5 U. 46.5 H

[56] References Cited UNITED STATES PATENTS 3,355,406 I 1/1967 Cekada, .lr 260/29.2 3,433,780 3/l969 Cekada, Jr. et al. 260/29.2 3.450.672 6/l969 Merrill 260/46.5 3,489,782 l/l970 Pruvost et al. 260/448.2

OTHER REFERENCES Barry et al., Crystalline Organosilsesquioxanes, American Chemical Society Journal. Vol. 77, pages 4248 to 4252. Aug. 20. i955 Primary E.tan|iner-- Donald E. Czaja Assistan! Examiner-M. l. Marquis All0fli Laurence R. Hobey and Roger H. Borrousch ORGANOSILSESQUIOXANES This application is a division of application Ser. No. 804,366, filed Feb. 26, 1969, now U.S. Pat. No. 3,489,782, issued Jan. 13, 1970, which is a continuation of application Ser. No. 558,614, filed June 20, 1966, now abandoned.

The present invention relates to polycondensates prepared from silanes having hydrolyzable substituents.

It is known that the triand tetrachlorosilanes are formed, for example, from the reaction of silicon with alkyl or aryl chlorides at the same time as the monoand dichlorosilanes. Depending on the operating conditions and the catalysts employed, the proportions of triand tetrachlorosilanes will vary and may go as high as 25 percent by weight of the total silanes fonned. However, the use of these triand tetrachlorosilanes is very much diminished because their hydrolysis, according to the conventional methods carried out in a heterogeneous medium at the interface of two phases, is violent, irregular and proceeds with complex reactions which provoke localized elevations of temperature which leads to unstable products or to gels without any worthwhile chemical or physical properties. The cohydrolysis of the triand tetrachlorosilanes with monoor dichlorosilanes has been suggested to make the triand tetrachlorosilanes more useful, but until now only small proportions of triand tetrachlorosilanes have been used in the cohydrolysates. As the proportion of triand tetrachlorosilane is increased in the cohydrolysate, the easier the composition forms gels and the more difficult it is to eliminate the gel formation.

Conversion of the tri and tetrachlorosilanes into silanes having hydrolyzable substituents other than chlorine is also possible, but this conversion requires a supplementary operation and generally the presence of a hydrochloric acid acceptor, such as pyridine or ammonia, is necessary. Moreover, classical hydrolysis of such substituted silanes likewise, often lead to gels without any worthwhile chemical or physical properties.

It is also known that the conversion of triand tetrachlorosilanes to dichlorosilanes is possible, but this constitutes a supplementary operation which is onerous to realize.

An object of this invention is to provide new industrial products which are polycondensates obtained by hydrolyzing silanes having at least three hydrolyzable substituents.

The process described herein avoids the various serious inconveniences discussed above and permits obtaining directly nongelled compounds, economically, rapidly and simply, composed of or containing silane polycondensates wherein the starting silanes have at least three hydrolyzable substituents. The polycondensates of this invention are obtained by starting from one or more silanes having at least three hydrolysable substituents, alone or in a mixture with one or more silanes having at least three hydrolzable substituents. The silane polycondensates exhibit numerous and various properties which render them suitable for a number of industrial applications.

This invention relates to a solventless, time-stable, polymerizable polycondensate comprising at least 75 mol. percent of chemically combined RSiO units and flows at a temperature of from to I C. inclusive, where the organo radicals of polycondensate are attached to silicon by silicon-carbon linkages, R is selected from the group consisting of methyl radicals, vinyl radicals and hydrogen atoms and up to 25 mol percent of the units of the polycondensate being selected from the group consisting of Si0 units, (CH SiO units, CH (H)SiO units and (CH SiO units.

It has been found by elementary experimental analysis that the polycondensates are of the following average statistical composition based on one atom of silicon:

This average statistical unit formula reflects, in a rather unrealistic fashion, the complexity of the structure of the polycondensates of the present invention. it gives only the results of the macromolecules analysis, whose actual structure is very difficult to establish. In these polycondensates the number of silicon atoms in the macromolecule can vary widely and can attain values of the order of 5000.

In the average statistical composition R can be a monovalent radical such as a hydrogen atom or an organic radical bonded to the silicon atom by a silicon-carbon bond such as any monovalent hydrocarbon radical, such as an alkyl radical such as methyl, ethyl, isopropyl, tertiary butyl, hexyl, octyl, 2-ethylhexyl, l-isobutyl-3,S-dimethylhexyl, dodecyl, octadecyl and myricyl; and alkenyl radical such as vinyl, allyl, decenyl, hexadienyl and octadecenyl; a cycloalkyl radical such as cyclopentyl, cyclohexyl and methylcyclohexyl; a cycloalkenyl radical such as cyclopentenyl, cyclohexenyl, cyclo-2,4-hexadienyl and cyclo-l,4-pentadienyl; an aryl radical such as phenyl, naphthyl and xenyl; an aralkyl radical such as benzyl, phenylethyl and xylyl; an alkaryl radical such as tolyl, ethylphenyl, dimethylphenyl, diethylphenyl, methylnaphthyl, propylxenyl. The monovalent hydrocarbon radicals can be substituted by groups such as halogenated, nitrated, sulfonated, sulfoxylated, carboxylated and thus monovalent substituted hydrocarbon radicals are also represented by R such as chloromethyl, 3,3,3-trifluoro-propyl, 3,3,4,4,5,5,5- heptafluoropentyl, a,,B,B-trifluoro-a-chlorocyclobutyl, 3,4- dibromocyclohexyl, 2-iodocyclopentene-3-yl, perchlorophenyl, B-nitroethyl, 'y-nitropropyl, nitrophenyl, (methylsulfonyl)ethyl, l-(propylsulfonyl)butyl, meta(methylsulfo)phenyl, B-carboxyethyl, y-carboxypropyl, B-(chlorocarboxy)ethyl, ethylcarboxyethyl and acetoxyethyl. R also represents a cyanoalkyl radical such as B-cyanoethyl, B-cyanopropyl, ycyanopropyl, w-cyanobutyl, a-cyanobutyl, and w-cyanooctadecenyl.

The silicon atoms in a single polycondensate can have R substituents which are alike or different from one silicon atom to the other. Moreover, the R substituents of a single silicon atom can be alike or different. The polycondensate is at least mol. percent RSiO, where R is methyl, vinyl or a hydrogen atom.

In the average statistical composition, X phenylethoxy a monovalent reactive radical such as a hydroxyl radical; a halogen atom such as chlorine, bromine, iodine and fluorine; an alkoxy radical such as methoxy; ethoxy, propoxy, butoxy, 4-one-2-methyl-2-pentoxy; an alkenyloxy radical such as allyloxy, 2-butenyloxy and pentenyloxy; a cycloalkoxy radical such as cyclobutoxy, cyclohexoxy and cyclopentoxy; a cycloalkenyloxy radical such as cyclobutenyloxy and cyclopentenyloxy; an aryloxy radical such as phenoxy, naphthoxy and xenoxy; an aralkoxy radical such as phenylethoxy and phenylpropoxy; phenylethoxy alkaryloxy radical such as methylphenoxy and dimethylphenoxy. The various organic radicals as shown above for X can also be substituted, for example, by halogen atoms, hydroxyl radicals, ethers, esters, nitriles, acid radicals. The substituted organic radicals can be, for example, 2-chloropropoxy, 3,3,3-trifluoropropoxy, 2-(ethoxy)ethoxy, 2-(ethoxy)propoxy, 3-(cyano)propoxy, and 3-(carboxy)propoxy. X can also represent any acid hydrolyzable radicals such as acetoxy, methylacetoxy, 2-ethylhexylacetoxy, sulfuric, organosulfuric, organosulfonic, as well as any basic hydrolyzable group such as amino, dimethylamino, ethylpropylamino, and hydrazine.

The silicon atoms in a single polycondensate can carry X substituents which are alike or different from one silicon atom to the other. Moreover, the X substituents on the same silicon atom can be the same or different.

The fact that R and X can be different from one silicon atom to another of a single macromolecule in a given polycondensate, signifies the presence of copolycondensates, that is, polycondensation products of at least two monomers.

The best process for the preparation of the polycondensates of the present invention comprises dissolving in a polar organic solvent at least one silane as defined below, hydrolyzing by contacting the silane with a hydrolyzing agent in a single homogenous liquid phase, thereafter, adding to the single homogeneous liquid phase and maintaining same, at least one silicon compound selected from the group consisting of a silane as defined below and a hydrolyzed product of at least one silane as defined below, maintaining a single homogeneous liquid phase during the dissolving step and the hydrolysis step and separating a polycondensate formed by the hydrolysis from at least any remaining hydrolyzing agent.

For the purpose of this invention the term hydrolyzing agent will mean, composed of or containing water such as water or water in an organic solvent or a product capable of freeing water, for example, hydrogen peroxide, an alcohol or a base reacted with an acid.

The initial compound to be subjected to hydrolysis by the process of the present invention can be a silane having from one to four inclusive hydrolyzable substituents. Each of the hydrolyzable substituents can be monovalent radicals such as halogen atoms, alkoxy radicals, alkenyloxy radicals, cycloalkoxy radicals, cycloalkenyloxy radicals, aryloxy radicals, aralkoxy radicals, alkaryloxy radicals, the foregoing organic radicals substituted with halogen atoms, hydroxyls, ethers, esters, nitriles and acid radicals, any acid hydrolyzable radical and any basic hydrolyzable radical. Examples of each are shown above for X. Any of the hydrolyzable substituents on a single silicon atom can be alike or different.

When a number of hydrolyzable substituents is less than four, the complement of four represents the number of nonhydrolyzable substituents which are described above for R. Any of the nonhydrolyzable substituents of a single silicon atom can be the same or different.

Among the substituted silanes corresponding to this definition, examples are: trichlorosilane, tetrachlorosilane, trimethylchlorosilane, methyltrichlorosilane, vinyltrichlorosilane, phenyltrichlorosilane, the distillation residue of chlorosilane synthesis formed from mixtures of various chlorosilanes and often rich in hydrolyzable chlorine, tertiary butyltrichlorosilane. 2-ethylhexyltribromosilane, octadecyltrichlorosilane, decenyltriiodosilane, cyclopentenyldiethoxychlorosilane, phenyldiethoxychlorosilane, benzyltrichlorosilane, 3,3,3-trifluoropropyltrichlorosilane, 3,3,4,4,5,5,5-heptafluoropentyltriiodosilane, B-cyanopropyltrichlorosilane, triiodosilane, methyltriacetoxysilane, bis(acetoxyethyl)phenylchlorosilane, bis(chlorocarboxyethyl) benzylchlorosilane, methylmonoacetoxydichlorosilane, methyldichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, methylpropyldodecyltri( 2-ethoxypropoxy)silane, myricyltri( 3- cyanopropoxy )silane, allyltri( 3-carboxypropoxy)silane, cyclohexyltri( methylacetoxy )silane, octadecenyltrisulfatesilane, cyclopentyltrihydrazinosilane, methylcyclohexyltrimethoxysilane, cyclohexenyldimethyltrimethoxysilane, cyclo-2,4-hexadienyltriisopropoxysilane, cycle-1,4-

pentadienyltrimethoxysilane, xenyltrimethoxysilane, trimethyl-(4-one-2-methyl-2-pentoxy)silane, phenylethyltripentenyloxysilane, tetracyclobutoxysilane, tetracyclopentoxysilane and (ethylphenyl )dimethyl(dimethylamino)silane.

The various hydrolyzable silanes as defined above can be hydrolyzed alone or in combinations of two or more. Thus it is possible to cohydrolyze two or more mono-, dior trichlorosilanes, or even mixtures of any of them and tetrachlorosilane. Examples of these combinations are: methyltrichlorosilane and trichlorosilane, methyltrichlorosilane and dimethyldichlorosilane, methyltrichlorosilane and tetrachlorosilane, phenyltrichlorosilane and dimethyldichlorosilane, methyltrichlorosilane and methyldichlorosilane, vinyltrichlorosilane and methyldichlorosilane, methyltrichlorosilane and vinyltrichlorosilane and methyldichlorosilane, methyltrichlorosilane and phenyltrichlorosilane and dimethyldichlorosilane, vinyltrichlorosilane and 3,3,3-trifluoropropyltrichlorosilane, [3- cyanopropyltrichlorosilane and triiodosilane, phenyltriethoxysilane and dimethyldichlorosilane and vinyltriethoxysilane.

The proportion of any of the initial silanes in the mixture to be cohydrolyzed can vary greatly. Depending on the desired final properties, it is possible to vary the structure and the respective proportion of any of the components. For example, the presence of a silane having four hydrolyzable substituents will increase the chemical activity of the polycondensate, because of the high proportion of silanol groups developed by the latter. Likewise, the presence of trihalogenosilanes contributes great chemical activity to the polycondensate because of the SiH bonding. Vinylsilanes contribute the usual properties of polymerization and copolymerization of the CH CH group. Phenylsilanes will augment the thermal stability of the polycondensates.

In the following by the expression silane, it is meant any compound corresponding to the definition given above, as well as a mixture of two or more of these compounds.

The process for the preparation of the polycondensates also includes a process wherein the hydrolysis of the silanes have started which can be either a partial or total hydrolysis and at a predetermined moment during the course of said hydrolysis at least one silane, which has been previously solvated in a polar solvent, is introduced in such a way that there is always only a single liquid phase and the hydrolysis is continued.

This hydrolysis can be pursued until it is terminated or a solvated silane which is the same or different from that preceding can be added to the hydrolysates while continuing the hydrolysis until it is terminated. In this manner one can proceed to a number of stages, intervening one or more grafting reactions in the course of a given hydrolysis.

The process includes still another variation wherein instead of the addition of silanes as discussed above, silanes are added which are already polycondensed or copolycondensed according to the classical methods of hydrolysis or better, according to the method of the present invention are added during the course of the hydrolysis. These polyand copolycondensates can be identical or different from the silanes in the course of hydrolysis. Examples of these polycondensates and copolycondensates are: hexamethyldisiloxane, bis(trimethylsiloxy)dimethylsilane, bis(dimethylvinylsilyl)oxide, bis(dimethylvinylsiloxy)dimethysilane, bis(dimethylsilyl)oxide, bis(dimethylsiloxy)-dimethylsilane, bis(methylsiloxy)monoethylsilane, tris(trimethylsiloxy)methylsilane, tris(trimethylsiloxy)-vinylsilane, tris(dimethylvinylsiloxy)vinylsilane, tris(dimethylsiloxy)methysilane, tetrakis(trimethylsiloxy)silane, tetrakis(dimethylsiloxy)silane, tetrakis(dimethylvinylsiloxy)silane, as well as siloxane chains having reactive groups such as hydroxyls or hydrolyzable groups. An example of the process is the addition of hexamethyldisiloxane to a mixture of methyltrichlorosilane and vinyltrichlorosilane during the course of the hydrolysis.

Further, silanes and/or polycondensates and/or copolycondensates can be incorporated in a polycondensate or copolycondensate issuing from a total or partial hydrolysis or cohydrolysis described above. This addition of silanes, polycondensates or copolycondensates during the course of or after the hydrolysis constitutes a means of grafting the polycondensates formed, consecutively to the various successive hydrolysis in the midst of the reaction mixture.

It is remarkable that the monovalent substituted hydrocarbon radical substituent which is bonded to the silicon atom through silicon-carbon bonds of the silane can sometimes be itself reactive to the silane, or the hydrolysis agent, or even to the secondary product which is formed. This leads to more simultaneous reactions, as for example, the hydrolysis of the silane on the one hand and the formation of a new function on the other hand. Thus, for example, if the monovalent radical substituent is an acid chloride or an ester there is simultaneous hydrolysis of the hydrolyzable functions bonded to the silicon atom and of the acid chloride or the ester to form the polycondensate sought and the hydrolyzed radicals of the organic functions, that is to say, the corresponding organic acid and/or the silicic ester, according to the operating conditions.

The solvation of the silane used provides a means for avoiding direct attack by the hydrolyzing agent on the silane and thus a controlled rather than very exothermic hydrolysis is obtained. Solvation of the silane is obtained with the aid of polar organic solvents possessing properties which cause the polar organic solvent to attach to the silicon atom of the silanes used, by physico-chemical phenomena characteristic of solvation. The polar organic solvent molecules solvated with the silicon atom are only displaced by molecules which are more polar than they are, for example, water.

The polar organic solvents which are particularly suitable for the solvation of the silanes are composed principally of oxygen or halogen containing organic compounds. Examples of such organic compounds are: ethers such as ethylether, butylether, tetrahydrofuran, diethylCarbitol and dioxane; ketones such as acetone, acetylacetone, methylethylketone and methylisobutylketone; halides such as chlorobenzene, carbon tetrachloride, perchloroethylene, trichloroethylene and methylene chloride; alcohols such as methanol, ethanol, propanol, butanol; alcohol ketones and alcohol aldehydes such as 4-methyl-4-ol-2-pentanone, 4,6-dimethyl-4-ol-3- isopropyl-Z-heptanone, 3-ol-butanal; polyols such as ethylene glycol, propylene glycol, butylene glycol; and ether alcohols such as Carbitols, Cellosolves and compounds containing one or more sulfur and/or nitrogen atoms such as diethylsulfide, diethylsulfinone, pyridine and a-picoline.

These various polar organic solvents can be employed singularly or in various combinations or even in mixtures with nonpolar organic solvents of the aromatic or aliphatic series which are miscible with the polar organic solvents. Examples are toluene, xylene, naphtha solvents, mineral spirits, white spirit and hexane. By using nonpolar organic solvents it is possible to regulate the polarity of the mixture for the best effect. Thus, one can use an acetone-toluene mixture which is particularly efficacious, economical and easy to employ.

In the case where one of the polar or nonpolar organic solvents used, displays reactivity toward the hydrolyzable substituents of the silane and particularly toward the halogen atoms, it is possible to have the water and the solvent acting on the silane simultaneously to prepare in situ, in the course of the hydrolysis, a polycondensate possessing new hydrolyzable substituents or not. The solvents best suited for the preparation of such polycondensates are most notably represented by the alcohols and polyols already mentioned in the category of solvents useful for the solvation of the silanes.

The solvation is, therefore, obtained by dissolving the silane in one of the polar organic solvents defined above in the nonlimiting list. The silane is generally dissolved at a temperature bordering ambient temperature. Nevertheless, the process operates at temperatures which are lower than ambient or at higher temperatures going up to boiling temperature of the solvent(s) used.

The quantity of the polar organic solvent required for the solvation depends on the nature of the silane and on the formation of the homogeneous liquid system. It can vary within wide limits of 0.5 to 10 mols, preferably between 2 and 5 moles of polar organic solvent per reactive function bonded to the silicone atom of the initial silane molecule to be hydrolyzed.

The quantity of the nonpolar organic solvent, which can be used to obtain a better homogenization of the reaction medium, can also vary between wide limits going from 0 to molar quantities equal to those of the polar organic solvent.

The proportion of the hydrolysis agent to be used, based on the silane, varies according to the products which are to be obtained. Thus, while it is possible to operate with less than the stoichiometric amount of hydrolyzing agent, incompletely hydrolyzed products are obtained. On the other hand, an excess of hydrolyzing agent, up to as much as 5-6 times the stoichiometric quantity, leads to completely hydrolyzed and slightly condensed products. Between these two extremes there is a whole family of intermediate products which can be obtained. The amount of hydrolyzing agent is preferably from 0. l to two times the stoichiometric amount.

The hydrolyzing agent can be added to the previously solvated silane. it is also possible to mix the solvated silane with a solution composed of the solvent or a mixture of solvents and the hydrolyzing agent. The silane can also be added to the solvent or the mixture of solvents previously added to the hydrolyzing agent, but in this case the solvent is in excess in relation to the hydrolyzing agent, preferably at least two times the amount of hydrolyzing agent, and because of the strong polarity of the medium the action of the solvent on the silane proceeds directly to the hydrolysis reaction.

The temperature at which the hydrolysis takes place affects the speed of the reaction and consequently the contact time of the reactants. It can vary between rather wide limits without, however, surpassing the ebullition temperature of the reaction medium. Preferably, one operates at temperatures which are near ambient temperature. it is obvious that one can operate at temperatures which are lower than ambient temperature, going as far as 60 C. However, the speed of the reaction diminishes with reduced temperature and reaching these low temperatures requires supplementary and onerous apparatus, and the interest in operating at such temperatures is not often justified.

After mixing the reaction products, the desired polycondensate is formed rapidly. Reaction time, easily determined for instance by measuring the electrical conductivity of the solution, is generally between 10 seconds and 10 minutes. Under the operating conditions, the product formed can evolve in the course of time but the total contact time of the reaction products is limited to less than 1 hour and 30 minutes, and preferably less than 15 minutes.

More advantageously, the hydrolysis is accomplished continuously which gives regular and homogeneous production and permits separation of the polycondensate as it is formed, thus avoiding evolution of the polycondensate and a loss of time. This is particularly useful in the case of grafting. ln effect, the silane or silanes are added while the polycondensate is forming, solvated with the graft and hydrolyzed. While the new polycondensate is obtained, more can be added and so on. lt is also possible to add another solution in which a polycondensate is just being formed.

At the end of the hydrolysis, the reaction medium contains the polycondensate formed in solution, as well as the secondary reaction products. The nature of these secondary products obviously depends on the initial hydrolyzable substituent. For example, when a halosilane is hydrolyzed the corresponding hydrogen halide is obtained. Likewise, with an alkoxysilane or an acyloxysilane, one obtains the corresponding alcohol or organic acid respectively.

At the end of the contact time for the reactants, the secondary products and the polycondensates are separated. This separation is accomplished, depending on the secondary product formed, particularly by one of the following methods which are examples of excellent separation methods.

(a) A solution of a neutralizing agent such as sodium carbonate, calcium carbonate, ammonium carbonate, ammonia, sodium, potassium, pyridine, a-picoline, or any organic base is added in the forms of a powder, a solution, an aqueous dispersion or a liquid. This addition fosters the separation of the solution in two phases; one phase contains the secondary product and one phase contains the polycondensate sought. The neutralizing agent can be introduced at the same time as the reactants or in proportion to and as the formation of the acidity develops, permitting neutralization, in situ of all or part of the acid formed as desired. This has the advantage of ameliorating the regularity of the reaction and its control, principally in the case of very active products such as would be obtained from tetrachlorosilane or trichlorosilane.

Another method of separating the polycondensate from its solution is by (b) heating and distilling a fraction of the solution in order to disrupt the equilibrium of the solution and provoke a separation into two phases of the undistilled fraction. These two phases are then separated by decanting. The phase containing the polycondensate is practically free of any secondary product.

Separation can also be accomplished by (c) adding to the solution a quantity of water necessary to provoke separation into two phases: one phase formed of water, the secondary product and part of the solvents; and one organic phase composed of the other part of the solvents and the polycondensates.

A further example of a method for separating the polycondensate from its solution is (d) simultaneously extracting the secondary product and the polycondensate by the addition of water and a water-immiscible organic solvent such as toluene, xylene or white spirit.

Procedures (c) and (d) can be used only in the case of total hydrolysis. In effect, the addition of significant quantities of water will provoke the hydrolysis of the remaining hydrolyzable substituents, in the case of partial hydrolysis.

Where the secondary product of a total hydrolysis is an acid, the organic phase obtained in methods (b), (c) and (d) often necessitates a final neutralization effected either by washing with water, washing with the aid of a neutralizing agent, and particularly with bicarbonated water followed by washing with water, or by the addition of pure alkaline bicarbonates followed by washing with water.

In most cases the organic phase is subjected to distillation, which permits recovering the organic solvent on the one hand and the polycondensate on the other hand. When the polycondensate is particularly reactive, it is preferable to keep the organic phase in solution and eventually to concentrate it.

The process can be put into practice continuously or discontinuously (batch) in any apparatus permitting efficacious mixture of the products employed and rapid treatment of the solution obtained after reaction. To operate discontinuously, one can utilize, for example, a reactor mounted with an agitator in which the reactants are introduced in convenient quantities, stirred for a predetermined time, and then discharged. Among continuous apparatus one can use, for example, a reactor of relatively low capacity, feeding in reaction products at constant and rigorous rate by means of gauge pumps and following a continuous system of treating the solution. Such a system has the advantage of readily allowing variations in the contact times by regulating output of the pumps and the volume of the reactor.

In the case of additions by stages, the apparatus can advantageously carry between the reactor and the treating system a second reactor mounted with a product feed for grafting, regulated with a gauge pump. lf more grafts are to be carried out by stages, one can add as many reactors and feeders as there are products to graft.

The polycondensates and copolycondensates obtained can be in the form of liquids, plastic solids and rigid solids which are susceptible to further reactions depending on the nature of the starting product, the hydrolysis rate, the proportion and the nature of the polycondensed or grafted products. Thus,

one obtains: Polycondensates resulting from a total hydrolysis, that is, all the hydrolyzable substituents if the starting silanes are reacted, not possessing reactive groups are present in the form of fluids. Polycondensates are obtained by total hydrolysis, possessing frec OH groups. Such polycondensates range from viscous liquids to plastic solids, susceptible to polymerization by means of the free OH. Polycondensates are obtained by total hydrolysis, possessing free OH groups and/orESi-H bonds, reactive organic groups such as Si- CH=CH and/or -SiCH- CH C N. These polycondensates, ranging from the liquid fluids to the hard solid, are polymerizable and reactable with other compounds. Polycondensates, obtained by partial hydrolysis, are reactive, possess hydrolyzable groups and range from the fluid liquids to plastic solids. Polycondensates, obtained by partial hydrolysis, possess hydrolyzable substituents and E Si H bonds or reactive organic groups such as E Si CH=CH and E Si CH CHz-C N groups. These polycondensates range from the viscous liquids to the plastic solids, are reactive and polymerize very easily.

All of these polycondensates will keep remarkably well, they are soluble in organic solvents if the latter do not act on the reactable groups bonded to the silicon atoms. Among these organic solvents are hydrocarbons such as toluene, benzene, xylene, light essences, and white spirit; alcohols such as methanol, ethanol, isopropanol and butanol; polyols such as ethylene glycol, propylene glycol, polyethylene glycols, polypropylene glycols; the corresponding ethers and esters of the polyols such as Cellosolves and Carbitols; ethers such as ethylether, propylether, ethylpropylether, dioxane and tetrahydrofuran; orthoesters such as ethylorthoformate, orthocarbonates, ethylorthosilicatc, ethylmethylsilicate as well as the derivative containingzSi-O-SiI-Ebonds such as bis(trimethylsilyl)oxide, bis(trimethylsiloxy)dimethylsilane and their higher homologues; esters such as ethyl acetate, propyl acetate, Z-ethylhexylacetate and any solvents generally used in silicone chemistry.

The polycondensates of this invention are useful in making electrical insulations, laminating compounds, molding compounds, protective coatings and water repellents. The polycondensates can also be used as intermediates which react with other silicone resins, and polydiorganosiloxanes as well as organic polymers and compounds.

The following examples are illustrative only and should not be construed as limiting the invention which is properly delineated in the appended claims.

EXAMPLE I The following hydrolysis was carried out continuously in an apparatus consisting of two containers equipped with rotameters and connected to a reactor of 150 cc. capacity, followed by an overflow tube connected to a continuous washing system.

Two-thousand nine-hundred and ninety grams (20 mols) of methyltrichlorosilane solvated at ambient temperature with 2,320 g. (40 mols) of acetone and 4,048 g. (44 mols) of toluene was placed in one of the containers. A solution of 7,500 g. mols) of acetone and 720 g. (40 mols) of water was placed in the second container.

The two solutions were simultaneously moved across the rotameters into the reactor at ambient temperature, so that both containers were completely empty at the same time after 2 hours which corresponded to a contact time for the reactants of 54 seconds. The reaction medium temperature was kept below 55 C. The homogeneous solution obtained after the reaction in the reactor, left the reactor via the overflow tube in a quantity equal to that of the two solutions entering the reactor and then the homogeneous solution arrived at the washing system. The solution was subjected to washing with water, which extracted the hydrochloric acid formed during the reaction and at the same time provoked the appearance of an organosilicon phase and an aqueous phase. The organosilicon phase was separated from the aqueous hydrochloric acid phase which contained a small quantity of each of the solvents by decanting.

The organosilicon phase was washed once with bicarbonated water, in order to insure neutralization and then with water. The resulting aqueous solutions were distilled and the solvents were recovered and recycled.

The organic solvents of the organosilicon phase were evaporated leaving the solventless polycondensate behind. One-thousand two-hundred and seventy-six grams of the polycondensate was obtained, which was a yield of 95 percent based on the initial chlorosilane. The polycondensate was a white crystalline solid with a point of fusion at 70 C. Analysis of the solid showed that the polycondensate contained 0.13 hydroxyl group and one methyl group per silicon atom.

The resulting polycondensate was soluble in any proportion in the usual alcohols, ethers, esters, commercial halogenated solvents, mixtures of these solvents with the hydrocarbon solvents such as toluene, benzene, xylene, light essences and white spirit. The polycondensate was equally soluble in glycols, polyglycols and their corresponding ethers and esters.

The polycondensate was a time stable product, for after many months it had the same solubilities in the same solvents.

The polycondensate was notably stable to heat. When heated in the presence of atmospheric air, it had a loss of 3 weight percent at 500 C., a 10 weight percent loss at 600 C. and a 10 weight percent loss at 1,000 C.

EXAMPLE 2 The hydrolysis was carried out in an apparatus identical to that described in example 1. A solution of 2,030 g. (35 mols) of acetone, 350 g. (3.8 mols) oftoluene and 162 g. (9 mols) of water was introduced into one of the containers.

Eight hundred and ninety-seven grams (6 mols) of methyltrichlorosilanc was solvated at ambient temperature in 1,740 g. (30 mols) of acetone and 350 g. (3.8 mols) of toluene. The resulting solution was introduced into the second container.

The reaction and the washing were carried out as described in example 1. The operation lasted 30 minutes and the contact time of the reactants was 40 seconds.

The solvents were evaporated at 374 g. of a solventless, white crystalline solid were obtained which corresponded to a yield of 93 percent by weight based on the initial chlorosilane. The polycondensate had a point of fusion of 90 C. Analysis of the polycondensate showed that the number of hydroxyl groups per silicon atom was 0.2 and the number of methyl groups per silicon atom was one.

The solubility of this polycondensate was the same as that of the product obtained in example 1.

The thermal stability of the polycondensate was about the same as the product of example 1 and showed a weight loss of 4 percent at 500 C. and a 1 1 percent at 600 C.

EXAMPLE 3 This process was carried out in an apparatus identical to that of example 1, but whose reactor had a 60 cc. capacity instead of 150 cc.

As described in example 1, a solution of 748 g. (5 mols) of methyltrichlorosilane solvated in 1,740 g. (30 mols) of acetone and 500 g. (5 mols) of methylisobutylketone was placed in one container and a solution of 144 g. (8 mols) of water, 2,030 g. (35 mols) of acetone and 500 g. (5 mols) of methylisobutylketone was placed in the other container.

The operation lasted 30 minutes which corresponded to a contact time of the initial products of about 17 seconds.

After washing and evaporating the solvents, 340 g. of a solventless, white crystalline solid was obtained which corresponded to a yield of 95 percent by weight based on the initial chlorosilane. At 120 C. the solid started to fuse which was rapidly followed by hardening.

The solubilities was practically identical to those of example 1, except that the solubility in pure hydrocarbon was slightly more difficult to obtain.

Analysis of the polycondensate showed that the resulting product possessed one methyl group per silicon atom and 0.5 hydroxyl group per silicon atom.

EXAMPLE 4 1n the same apparatus described in example 3, 810 g. (6 mols) of trichlorosilane solvated in 1,740 g. (30 mols) of acetone was placed in one container and 216 g. 12 mols) of water, 2,900 g. (50 mols) of acetone and 1,000 g. 10 mols) of methylisobutylketone was placed in the other container.

The addition lasted for 30 minutes which was a contact time of 14 seconds for the reactants. The temperature of the reactor was kept near 0 C. After washing and decanting as described in example}, 1,250 g. of a solution whose dry extract was 24 percent by weight was obtained, which corresponded to a yield of 94 percent by weight based on the initial chlorosilane.

Analysis of the solution showed that the product possessed 0.73 hydrogen atoms per silicon atom.

The polycondensate in solution possessed exceptional reactivity due to its rich content ofaSi-H bonds, a matter which made its manipulation and its use rather delicate.

EXAMPLE 5 Three thousand four hundred and eighty grams (60 mols) of acetone and 180 g. (10 mols) of water were placed in a 10 liter flask equipped with a stirrer and cooled by running water at ambient temperature.

Progressively, 807 g. (5 mols) of vinyltrichlorosilane was added so that the temperature of the reaction medium did not surpass 40 C. The addition was terminated after 30 minutes. At the end of the addition the homogeneous solution contained in the flask was emptied into a 20 liter flask equipped with a stirrer and containing 2,000 g. of toluene and 3,000 g. of water. The toluene extracted the polycondensate formed and a part of the acetone. The rest of the acetone and the hydrochloric acid formed was found in solution in the water.

The organic phase composed of toluene, acetone and the polycondensate (practically neutral) was completely neutralized by washing with bicarbonated water, and then washing with pure water. By evaporating the solvents, 385 g. of solventless, white crystalline powder was obtained which corresponded to a yield of 96 percent by weight based on the initial vinyltrichlorosilane.

Analysis of the polycondensate determined the elementary structure to be (CH =CHSiO O,, H.

The polycondensate melted between 75 and C. The weight loss and the solubilities are the same as those of example l.

EXAMPLE 6 This process was carried out as described in example 5 with 1,740 g. (30 mols.) of acetone and g. (10 mols) of water to which 1,057 g. (5 mols) of phenyltrichlorosilane was added. Six hundred and thirty-eight grams of a solventless, white crystalline powder was obtained which corresponded to a yield of 92.5 percent by weight based on the initial silane.

Analysis of the product showed that there were 0.22 hydroxyl group per silicon atom and one phenyl group per silicon atom.

EXAMPLE 7 A solution of 1,020 g. (6 mols) of tetrachlorosilane sol vated in 1,740 g. (30 mols) of acetone was placed in one container and a solution of 1,000 g. (10 mols) of methylisobutylketone, 2,900 g. (50 mols) of acetone and 216 g. (12 mols) of water was placed in another container in the same apparatus of example 3. The reactor was kept at 10 C. because the reaction was rather violent in spite of the protection given by the solvents.

In order to improve the control and the regularity of the reaction, one-quarter of the mols of the hydrochloric acid was neutralized in situ as they were fonned during the reaction by the addition of sodium carbonate.

The contact time for the initial reactants was 14 seconds. After washing and decanting as described in example 1,

EXAMPLE Example 1 was repeated except that the mols of methyltrichlorosilane was replaced by mixtures of variable propor- 1 15.0 g. of a solution of 26 percent dry extract was obtained 5 of mewyhndlflomslane as Show" z f which corresponded to a yield of 83.5 percent by weight based f e resudtmg ycdon T g ana yze an t e pomt O on the initial tetrachlorosilane. was etermme as 5 own 8 OH in the CH per 51 CHgSlC 1, S1014, polyconden- 1n the poly- Point of mols mols sate per Si condensate fusion, C. Appearance 19 1 0.2 0. 95 100-120 White crystalline solid. 2 0. 0. 9 (I) DO. 6 0. 4 0. 76 D0.

I Not clear.

The polycondensate in solution was very rich in hydroxyl groups bonded to the silicon atoms which-made it very reactive. Therefore, the usual reagents necessary for determining the hydroxyl groups would cause a polymerization which was more or less complete before the determination could be terminated merely by their presence.

EXAMPLE 8 This operation was carried out in mols) apparatus identical to that described in example 1. Two Thousand five hundred and eighty grams (20 mols) of dimethyldichlorosilane dissolved in 1,680 g. (29 mols) ofacetone and 1,840 g. (20 mols) of toluene was placed in one of the containers and a solution of 5,200 g. (90 mols) ofacetone and 540 g. (30 mols) of water was placed in the second container.

The reaction and the washing was carried out as described in example 1. The contact time for the reactants used was seconds.

The organic solution was distilled under a pressure of 20 mm. Hg obtaining two fractions: a first fraction of 1,600 g. distilling at 70 C. and composed principally of toluene, a second fraction of 700 g. distilling between 70 and 135 C. and composed of a polycondensate of cyclic structure having two methyl groups per silicon atom but no hydroxyl groups, and a residue of 423 g. ofa polycondensate which was a light amber fluid having a linear chain with two methyl groups per silicon atom and 0.13 hydroxyl group per silicon atom, and having a viscosity of 26 cs. at 25 C. determined with a Ubbelohde viscosimeter.

EXAMPLE 9 The hydrolysis of a chlorosilane distillation residue was carried out in an apparatus identical to that of example 1.

in one container a solution of 7,000 g. ofacetone and 705 g. of water was placed and in the other container, 2,000 g. of toluene and 3,000 g. of residue containing percent hydrolyzable chlorine was placed.

The process was carried out as in example 1. The hydrolysis temperature was less than 40 C. and the contact time for the reactants was seconds.

Two thousand grams of a polycondensate with a resinous aspect was obtained which had a hydroxyl group content of about 1 percent by weight and a content ofESiH bonds of 2 Examination of the results of the table showed that the number of hydroxyl groups and therefore the activity of the polycondensate was increased when the quantity of the initial tetrachlorosilane was increased.

EXAMPLE 1 l Using the same process and the same apparatus of example 1, a solution of 2,690 g. (18 mols) of methyltrichlorosilane and 271 g. (2 mols) of trichlorosilane solvated in 2,900 g. (50 mols) of acetone and 4,048 g. (44 mols) of toluene was contacted with a solution of 8,700 g. (150 mols) of acetone and 720 g. (40 mols) of water.

After washing and decanting, the solvents were evaporated from the organic phase and 1,102 g. of a solventless, white crystalline solid was obtained which corresponded to a yield of 83 percent by weight based on the initial silanes and which contained 0.08 hydroxyl group per silicon atom and 0.095 hydrogen atom (ESiH) per silicon atom.

Because of the presence of the hydroxyl groups and the E Si-l-l bonds, this product was especially reactive.

EXAMPLE 12 Example 11 was repeated by hydrolysis with 628 g. (4.2 mols) of methyltrichlorosilane, 244 g. (1.8 mols) of trichlorosilane in the presence of 4,465 g. (77 mols) of acetone, 1,100 g. (12 mols) oftoluene and 216 g. l2 mols) of water. Two hundred and ninety-six grams of a solventless, white crystalline solid was obtained which corresponded to a yield of 77 percent by weight based on the initial silanes. The polycondensate had 0.144 hydroxyl group per silicon atom and 0.30 hydrogen atom Si- H bonds) per silicon atom.

EXAMPLE 13 Example 1 was repeated, replacing the 20 mols of methyltrichlorosilane with a mixture of methyltrichlorosilane and dimethyldichlorosilane in variable proportions as indicated in the table below. The resulting solventless, polycondensates were analyzed and their points of fusion were determined. The results were gathered in the table below and for comparison OH per S1 in Point 01' luslon CHzSiCli, (CHahSlClz, the poly- 01 the polymols mols condensate condensate, Properties 0 0. 13 Crystalline solid. 0. 6 0. 13 50-90 D0.

1 0. 07 45-60 Slightly opaque,

solid.

18.6 1. 4 0. 076 16-20 Viscous liquid at 25 0., viscosity ca. 50,000 cs.

17 3 0.16 60-90 Slightly opaque,

solid.

percent by weight based on the polycondensate. The viscosity the same characteristics for the methyltrichlorosilane was about 12,000 cs. at 25 C. as determined with a Ubbelohde viscosimeter.

polycondensate prepared alone under the same conditions have been indicated.

EXAMPLE 14 The same apparatus of example 3 was used except the overflow tube entered a second reactor equipped with a connector attached to a container by means of a rotameter and an over flow tube which entered a third reactor identical to the second, whose overflow tube was connected to a continuous washing system.

Five thousand three hundred and eighty grams (36 mols) of methyltrichlorosilane and 646 g. (4 mols) of vinyltrichlorosilane were solvated in a mixture of 5,800 g. (100 mols) of acetone and 8,200 g. (89 mols) of toluene. The resulting solution wasintroduced into a container of the first reactor. The other container contained 17,400 g. (300 mols) of acetone and L440 g. (80 mols) of water.

The container of the second reactor contained 460g. .(4 mols) of monomethyldichlorosilane dissolved in 2,535 g. (44 mols) of acetone and the container of the third reactor contained 3,894 g. (24 mols) of hexamethyldisiloxane. The first two solutions were introduced into the first reactor at the same time. When this mixture reached the second reactor, the addition of the monomethyldichlorosilane was started, then at the entry of the third reactor, the addition of thehexamethyldisiloxane was started. The entry of each solution was regulated so that there was a contact time of 45 seconds in thefirst reactor, 30 seconds in the second reactor and 30 seconds in the third reactor. The solution entering the washing system was treated continuously as in example 1.

The final organosilicon solution was evaporated byheating at 250 C. where it was keptfor 1 hour.

The residue was composed of 3,472 g. of an oil with a density of l. 145 g./cc. and a viscosity of about 10,000 cs. at 25 C. which corresponded to a yield of 97 percent by weight based on the original reactants.

Analysis of the polycondensate showed 0.008 hydroxyl group per silicon atom, 0.06 hydrogen atom (ESL-H bond) per silicon atom and 0.08 vinyl group per silicon atom.

3.7 moles of the 24 initial moles of the hexamethyldisiloxane were grafted onto polycondensate. The rest of the hexamethyldisiloxane was recovered from the evaporation process.

EXAMPLE [5 The same apparatus as that described in example 14, but having only two reactors, was used.

Six hundred and eighty grams (4 mols) of tetrachlorosilane solvated in 4,000 g. (69 mols) of acetone was placed in one of the containers. The other container of the first reactor contained 2l6 g. (12 mols) of water and 986 g. (l7 mols) of acetone.

The container of the second reactor contained 2,916 g. l8 mols) of hexamethyldisiloxane.

The first two solutions were added into the first reactor at the same time. When the mixture entered the second reactor, the addition of the hexamethyldisiloxane was begun. The entry of each of these solutions was regulated so that there was a contact time of 60 seconds in the first reactor and of 2 minutes in the second reactor.

The solution was then washed continuously and neutralized as described in example l. A part of the solvent was evaporated and 320 g. of a solution with 75 percent dry extract was obtained having a viscosity of 7 cs. at 25C. Analysis of the polycondensate showed 0.0l hydroxyl group per silicon atom.

EXAMPLE l6 The process was carried out as described in example 3 with 290 g. (5 mols) of acetone, 416 g. l3 mols) of methanol and l08 g. (6 mols) of water placed in one container and 290 g. (5 mols) of acetone, 736 g. (8 ,mols) of toluene and l,000 g. of chlorosilane distillation residue containing 45 percent hydrolyzable chlorine placed in the other container. After washing continuously the final solution was evaporated and 982 g. of an oil was obtained which had a viscosity of 30 cs. at 25 C. and contained 30 percent-:Si-OCH, groups.

EXAMPLE 17 A mixture of 2,410 g. (50 mols) of 95 percent ethyl alcohol and 486 g. (27 mols) of water are added over aperiod of neutralization was terminated with sodium bicarbonate and the product was then filtered.

After the solvent was evaporated 2,000 g. of a colorless oil with a viscosity of 40 cs. at 25 C. vwas obtained, which corresponded toa yield of 83.5 percent byweight based on the original silane.

Analysis of this oil showed the presence of one ethoxy group per two silicon atoms and one methylgroup per silicon atom.

EXAMPLE 18 A solutionof l,492 g. of 95 percent ethyl alcohol and 38 g. of water and a solution of 1,794 g. (12 mols) of methyltrichlorosilane solvated in 696 g. (l2 mols) of acetone were simultaneously placed in a5 liter flask equipped with an agitator. The temperature of the reaction medium was kept at 10 C. It was heated and a part of thesolvent was distilled and two phases were thus obtained.

As in example 17, l ,000 got an oil was obtained which corresponded to a yield of 82.5 percent by weight based on the original silane. The oil had a'viscosity of l0 cs. at 25 C. and contained three ethoxy groups per four silicon atoms and one methyl group persilicon atom.

EXAMPLE 19 This process was carried out as described in example 1 with a solution of l,730 g. (10 mols) of methyldichloroacetoxysilane solvated in l,l60 g. (20 mols) of acetone and 2,024 g. (22 mols) of toluene in one container and a solution of 4,350 g. (75 mols) of acetone and 5.40 g. (30 mols) of water in the other container.

Six hundred and thirty-seven grams of a solventless, white crystalline solid was obtained identical to the polycondensate obtained in example 1, which corresponded to a yield of 95 percent by weight based on the initial silane.

EXAMPLE 20 This process was carried out as described in example 3 with a solution of l,l00 g. (5 mols) of methyltriacetoxysilane solvated in L740 g. (30 mols) of acetone and 460 g. (5 mols) of toluene in one container and a solution of I44 g. (8 mols) of water, 2,030 g. (35 mols) of acetone and 460 g. (5 mols) of toluene in the other container.

Three hundred and fifteen grams of a solventless, white crystalline solid was obtained which corresponded to a yield of percent by weight based on the initial silane., Analysis of the polycondensate showed that the product contained one methyl group per silicon atom and 0.05 acetoxy group per silicon atom.

EXAMPLE 21 When 20 mols of any one of the following silanes or silane mixtures are substituted for the methyltrichlorosilane of example 1 and the same process is followed, equivalent results are obtained.

A mixture of 1 mol of trimethylchlorosilane and 19 mols of vinyltrichlorosilane.

A mixture of 2 mols bis(acetoxyethyl)phenylchlorosilane and 18 mols of methyltriacetoxysilane, and

methy1tri( 2-ethoxyethoxy)silane.

We claim:

1. A solventless, time-stable, polymerizable polycondensate comprising at least 75 mole percent of chemically combined RSiO units and flows at a temperature of from 15 to 120 C. inclusive, where the organo radicals of the polycondensate are attached to silicon by silicon-carbon linkages, R is selected from the group consisting of methyl radicals, vinyl radicals and hydrogen atoms and up to 25 mole percent of the units of the polycondensate being selected from the group consisting of SiO units, (CH ),SiO units, CH (H)SiO units and (CH,) Si O units.

2. The solventless, time-stable, polymerizable polycondensate of claim 1 in which all of the R groups are methyl radicals.

3. The polycondensate of claim 2 having from 0.75 to 1.15 methyl radicals per silicon atom and from 0.07 to 0.5 hydroxyl groups per silicon atom.

4. The polycondensate of claim 3 having one methyl radical per silicon atom and 0.13 hydroxyl group per silicon atom.

5. The polycondensate of claim 3 having one methyl radical per silicon atom and 0.2 hydroxyl group per silicon atom.

6. The polycondensate of claim 3 having one methyl radical per silicon atom and 0.5 hydroxyl group per silicon atom.

7. The polycondensate of claim 3 having 0.95 methyl radical per silicon atom and 0.2 hydroxyl group per silicon atom.

8. The polycondensate of claim 3 having 0.9 methyl radical per silicon atom and 0.25 hydroxyl group per silicon atom.

9. The polycondensate of claim 3 having 0.75 methyl radical per silicon atom and 0.4 hydroxyl group per silicon atom.

10. The polycondensate of claim 3 having 1.03 methyl radicals per silicon atom and 0.13 hydroxyl group per silicon atom.

11. The polycondensate of claim 3 having 1.05 methyl radicals per silicon atom and 0.07 hydroxyl group per silicon atom.

12. The polycondensate of claim 3 having 1.07 methyl radicals per silicon atom and 0.075 hydroxyl group per silicon atom.

13. The polycondensate of claim 3 having 1.10 methyl radicals per silicon atom and 0.11 hydroxyl group per silicon atom.

14. The polycondensate of claim 3 having 1.15 methyl radicals per silicon atom and 0.15 hydroxyl group per silicon atom.

15. The polycondensate of claim 1 of the formula (CH 1.5)7 0.5

16. The polycondensate of claim 1 having CH SiO units and HSiO units and having 0.095 silicon-bonded hydrogen atom per silicon atom and 0.08 hydroxyl group per silicon atom.

17. The polycondensate of claim 1 having CH SiO units and HSiO units and having 0.30 silicon-bonded hydrogen atom per silicon atom and 0.144 hydroxyl group per silicon atom.

18. The polycondensate of claim 1 which consists essentially of 71.6 mole percent CH SiO units, 8.0 mole percent CHfCHSiO units, 6.0 mole percent CH (H)SiO units and 14.4 mole percent (CH;) -,SiO units and having 0.008 hydroxyl groups per silicon atom.

19. The polycondensate of claim 1 having 0.5 ethoxy group per silicon atom and one methyl radical per silicon atom.

20. The polycondensate of claim 1 having 0.75 ethoxy group per silicon atom and one methyl radical per silicon atom.

21. The polycondensate of claim 1 having 0.05 acetoxy group per silicon atom and one methyl radical per silicon atom.

22. A solventless, polymerizable polycondensate consisting essentially of chemically combined SiO units and HSiO units and having 0.73 silicon-bonded hydrogen atoms per silicon atom. 

2. The solventless, time-stable, polymerizable polycondensate of claim 1 in which all of the R groups are methyl radicals.
 3. The polycondensate of claim 2 having from 0.75 to 1.15 methyl radicals per silicon atom and from 0.07 to 0.5 hydroxyl groups per silicon atom.
 4. The polycondensate of claim 3 having one methyl radical per silicon atom and 0.13 hydroxyl group per silicon atom.
 5. The polycondensate of claim 3 having one methyl radical per silicon atom and 0.2 hydroxyl group per silicon atom.
 6. The polycondensate of claim 3 having one methyl radical per silicon atom and 0.5 hydroxyl group per silicon atom.
 7. The polycondensate of claim 3 having 0.95 methyl radical per silicon atom and 0.2 hydroxyl group per silicon atom.
 8. The polycondensate of claim 3 having 0.9 methyl radical per silicon atom and 0.25 hydroxyl group per silicon atom.
 9. The polycondensate of claim 3 having 0.75 methyl radical per silicon atom and 0.4 hydroxyl group per silicon atom.
 10. The polycondensate of claim 3 having 1.03 methyl radicals per silicon atom and 0.13 hydroxyl group per silicon atom.
 11. The polycondensate of claim 3 having 1.05 methyl radicAls per silicon atom and 0.07 hydroxyl group per silicon atom.
 12. The polycondensate of claim 3 having 1.07 methyl radicals per silicon atom and 0.075 hydroxyl group per silicon atom.
 13. The polycondensate of claim 3 having 1.10 methyl radicals per silicon atom and 0.11 hydroxyl group per silicon atom.
 14. The polycondensate of claim 3 having 1.15 methyl radicals per silicon atom and 0.15 hydroxyl group per silicon atom.
 15. The polycondensate of claim 1 of the formula (CH2 CHSiO1.5)7O0.5H.
 16. The polycondensate of claim 1 having CH3SiO1.5 units and HSiO1.5 units and having 0.095 silicon-bonded hydrogen atom per silicon atom and 0.08 hydroxyl group per silicon atom.
 17. The polycondensate of claim 1 having CH3SiO1.5 units and HSiO1.5 units and having 0.30 silicon-bonded hydrogen atom per silicon atom and 0.144 hydroxyl group per silicon atom.
 18. The polycondensate of claim 1 which consists essentially of 71.6 mole percent CH3SiO1.5 units, 8.0 mole percent CH2 CHSiO1.5 units, 6.0 mole percent CH3(H)SiO units and 14.4 mole percent (CH3)3SiO0.5 units and having 0.008 hydroxyl groups per silicon atom.
 19. The polycondensate of claim 1 having 0.5 ethoxy group per silicon atom and one methyl radical per silicon atom.
 20. The polycondensate of claim 1 having 0.75 ethoxy group per silicon atom and one methyl radical per silicon atom.
 21. The polycondensate of claim 1 having 0.05 acetoxy group per silicon atom and one methyl radical per silicon atom.
 22. A solventless, polymerizable polycondensate consisting essentially of chemically combined SiO2 units and HSiO1.5 units and having 0.73 silicon-bonded hydrogen atoms per silicon atom. 